Pressure wet-fixation of resins in cellulosic fabrics by the action of heat and pressure



United States Patent U.S. Cl. 11765.2 2 Claims ABSTRACT OF THEDISCLOSURE The purpose of this invention is to wet-fix N-methylol resinsin cellulosic fabrics by the action of heat and pres sure to producefabrics capable of resisting wrinkling or mussing throughout areasonable wear life. Pressure wetfixation is accomplished by either oftwo methods, a onestep or alternatively a two-step process. Theadvantage of the two-step padding method over that known in the priorart as wet-fixation is a reduction in the time required to wet-fix theN-methylol resins in the cellulosic fabrics. The other simpler method,the one-step padding method, has the advantage that it eliminates one ofthe padding, washing and drying steps.

A nonexclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

Because of their poor resiliency, cellulosic textile fabrics tend tobecome wrinkled in use and acquire a mussed or unplesant appearance. Toovercome this objectionable property, it has been the practice to treator finish cellulosic textiles with the methylol derivatives of organicnitrogen compounds, such as urea, ethyleneurea, guanidine, maleamine,and the like. These agents produce a finished cellulosic fabric that hasimproved resistance to wrinkling or mussing and give to the fabric theability to dry smooth after laundering. A serious drawback results sincethe cellulosic fabrics are damaged during these treatments, therebyreducing the wear life of the treated cellulosic fabrics.

A wet fixation method was devised by Workers of the National CottonCouncil and Harris Research Laboratories to overcome damage to thecellulosic fabrics during treatment. In this method of treatment, thecellulosic fabrics are impregnated with a solution which deposits resinsinside the wet, swollen cellulosic fiber. This is accomplished bypadding an N-methylol resin-mineral acid solution on the fabric, heatingthe fabric in a closed or semiclosed container for 15 minutes at 180 F.,neutralizing in sodium carbonate solution, washing, and drying. Theheating re-- sults in deposition of the resin in the fiber in such amanner that it is not removed by washing and so sustains the fibers in asomewhat swollen condition. Subsequent application of a crosslinkingcatalyst, followed by a hightemperature dry cure, results in only modestloss of fabric strength as compared with conventional pad-dry-cureprocessing.

According to the developers of the wet-fix process, the important factorin arriving at good strength properties of the finished fabric and highlevels of fabric performance, both in resistance to wrinkling and goodcrease retention, is the use of two resin components. One of these,called a polymer builder, acts to swell the fibers and keeps them in aswollen state (melamine derivatives are 3,523,033 Patented Aug. 4, 1970particularly effective in this regard); the second component, primarilya crosslinking agent for cotton, contributes only moderately to theswelling of the fiber but enhances wet wrinkle recovery and, oncecatalyzed and dried, imparts high dry wrinkle recovery to the fabric(dimethyloldihydroxyethylene urea and dimethylol carbamates are goodexamples of this class).

In mill trials cellulosic fabric is impregnated with the resin solution,made into rolls, sealed, and rotated overnight while wet fixation istaking place. Difficulty has been experienced in achieving good yarnpenetration in plant runs. In short, the laboratory procedure of wet-fixis not directly applicable to mill runs; in addition, it requires moresteps than the procedures normally used in the prior art to achieveresistance to wrinkling and mussing. Mill runs have not given thedesired yarn penetration, nor is the method applicable to continuousprocessing.

For the purposes of the instant invention, the fabrics used were an x 80cotton printcloth (3.2 oz./sq. yd.) which was desized, scoured, andbleached; and a white, 7 02., cotton twill from Testfabrics, Inc.(#413).

The press used was a standard hot-head press on which I the time thepress was closed could be manually controlled. The air pressure wasadjustable, but the steam pressure was constant; however, the steamcontrolled temperature increased with the length of time that the presswas closed.

The properties of the cellulosic fabrics which were finished by themethods of this invention are illustrated in the following discussionand examples. All parts and percentages described are by weight. Thedegree of wrinkle resistance in the finished textile is shown by thewrinkle recovery angle, determined by the American Society for TestingMaterials Test Dl424-56T. The tearing strength of the fabrics isobtained by the Elmendorf method, American Society for Testing MaterialsTest D1424-63. The Stoll fiex abrasion resistance of the fabrics isdetermined by the American Society for Testing Materials Test D1175-64T. The laundry tests with simulated trouser cuffs were evaluatedafter repeated laundry wash-tumble dry cycles. A four-pound load waswashed in 18 gallons of water on a normal laundry cycle set for eightminutes using a wetting agent as detergent. Water temperature controlwas set for a hot (61 C.) wash and warm rinse. After washing, the cuffswere tumble dried for 30 minutes in a gas-heated dryer at about 60 C.Each cuff was then inspected for abrasive damage. The breakage of eithera warp or filling yarn was classified as minor damage. The breakage ofboth a warp and a filling yarn to form a detectable hole was classifiedas major damage. Wash-wear ratings were obtained by the MonsantoOverhead Lighting method.

The mechanism by which the resins mentioned produce the wrinkleresistant and smooth drying properties without seriously affecting thewear life of the cellulosic fabric in our new pressure wet-fix processis essentially the same as that described previously for the 'Wet-fixprocess. That is, N-methylol resins are deposited inside the wet,swollen cellulosic fiber in such a manner that they are not removed bywashing, thereby sustaining the fibers in a somewhat swollen condition.However, by reason of the fact that pressure is applied, resinpenetration is accomplished in a shorter time; in addition, theN-methylol resins penetrate the fibers evenly, resulting in an evendistribution of resin throughout the fabric.

An object of this invention is to provide a method for treating orfinishing cellulosic textiles whereby the textile is rendered resistantto wrinkling or mussing during use and will have improved smooth dryingproperties after laundering without impairing the wear life of thecellulosic fabric. This was accomplished by padding cellulosic fabricswith solutions of the following compositions:

(1) About from 5 to percent solids of a polymer builder of themethylated methylolmelamine type resin from the group consisting ofAerotex 23S, Aerotex M3, and Melrez MF, about from 5 to 10 percentsolids of a crosslinking resin, dimethyloldihydroxyethyleneurea(Permafresh 183), and about from 80 to 90 percent water. The solutionwas adjusted to about from pH 2 to pH 6 with hydrochloric acid andallowed to remain about 30 minutes at room temperature. The solution wasadjusted before padding to about from pH 2 to pH 6 with sodiumhydroxide, or alternatively.

(2) About 10 percent solids of a polymer builder,hexamethyoxymethylmelamine (Cymel 301) and about 10 percentdimethyloldihydroxyethyleneurea (Permafresh 183), 13.6 percent absoluteethyl alcohol, and 66.4 percent water. The solution was adjusted to a pHof about 6, if necessary and used for padding after thorough mixing atroom temperature.

After padding to about 80 percent wet pick-up with the selected treatingsolution, the fabrics were placed either in plastic bags or betweensheets of aluminum foil and pressed in a hot-head press for about from 1to 4 minutes under about from to 90 p.s.i. pressure with a temperatureincrease of about from 60 to 120 C., cooled in the container, and aftercooling the wet fabrics were washed. After drying, the fabrics werepadded with a solution containing about 4 percent magnesium chloridehexahydrate as the catalyst, about 2 percent polyethylene emulsion(Polymul CS81) as the softener, and 94 percent water. The fabrics weredried for about 7 minutes at about 60 Cv in a forced draft oven. Thefabrics were either cured in a forced draft oven for about from 3 to 5minutes at about 160 C. or stored for subsequent curing.

In the earlier experiments aluminum foil was used to seal in thevolatile components during pressing; however, plastic bags proved togive a more efficient seal, as the heat softened bag sealed itself underpressure. Since the heat softens the plastic bags during pressing, it isnecessary to insulate the bags from the press. A double thickness ofcloth on both sides of the plastic bag eliminated this problem. Fabricsremoved from the textiles whereby the textile is rendered resistant towrinkling or mussing during use and will have improved smooth dryingproperties after laundering without impairing the wear life of thecellulosic fabric. This was accomplished by padding a cellulosic fabricin a solution of the following compositions: about from 5 to 12 percentsolids of a polymer builder of the methylated methylolmelamine typeresin from the group consisting of Aerotex 23S and Aerotex M3, aboutfrom 5 to 12 percent dimethyloldihydroxyethyleneurea (Permafresh 183),about from 4 to 5 percent of a catalyst, magnesium chloride hexahydrate,about from 2 to 3 percent of a softener, polyethylene emulsion (PolymulCS81), and about from 69 to 84 percent water. The solution was at pH 6,and no adjustment was made during treatment of the fabric. After paddingto about 80 percent wet pick-up, the fabrics were placed in plastic bagsand pressed for about from 3 to 5 minutes under about 27 p.s.i. pressurewith a temperature increase of about from 60 to 115 C. On cooling, theheat sealed plastic bags were opened and the wet fabrics were driedabout from 5 to 10 minutes at about 60 C. in a forced draft oven. Thefabrics can be made into garments or stored for future garmentpreparation. Curing can be carried out in a forced draft oven at. about160 C. about from 3 to 5 minutes.

The data in Table I show that the dry (or conditioned) fabrics treatedby the pressure wet-fix method are of relatively low wrinkle resistanceafter the pressure wet-fix step. This is shown with treatment C. Thecured fabrics have conditioned wrinlele recovery angle values abovethose of the controls while the uncured are not improved. Fabricsremaining in the hot-head press for one minute at 88 p.s.i. pressureshowed some increase in conditioned wrinkle recovery angle over thevalves for the controls; the better conditions appeared to be 3 minutesin the hothead press at 27 p.s.i. pressure. Although fabrics wereallowed to remain in the hot-head press for 7 minutes at 27 p.s.i.pressure, the overall properties of the treated fabrics did not improve.Treatment D shows that as the time in the hot-head press increases, theconditioned and wet wrinkle recovery angles increase while the tearingstrength and abrasion resistance values decrease. Satisfactory resultswere obtained at pH 4 but there was no plastic bags were wet and limpwhile those removed advantage over that obtained at pH 6.

TABLE I.TWO STEP PADDING METHOD OF PRESSURE WET FIXATION ON 80 x 80COTTON PRINTOLOTH Pressure Time in wet-fix, Cure time Cure, ConditionedTearing Abrasion resist- Air prespress Temp percent at 160 0. percentWRA (w+f) Wet WRA strength, gins. ance flex cycles Treatment pH sure,p.s.i. (min) add on (min) add-on deg. (w+i) deg. (w.) (w.)

A. Average values of washed samples of Bil-square cotton printcloth, 3.2oz.lsq.yd., which had been caustic-boiled, bleached, and desized.

B. Average values of unwashed samples of -square cotton printeloth, 3.2oz./sq.yd., which had been caustic-boiled, bleached and desired.

C. These 80-square cotton fabrics were padded in a solution consistingof Aerotex 238 (a methylated methylolmelamine) (10% solids), Permafresh183 (a dhnethyloldihydroxyethyleneurea) (10% solids), and water (80%).The solution was adjusted to pH 2 with H01, allow ed to stand 30 minutesat room temperature and adjusted to pH 6 with NaOH before three drops ofTriton X- were added to the pad bath per each 100 grams of solutionused. A catalyst-softener solution consisting of Mgfrom the aluminumfoil were damp and slightly stiff in some cases. The stiifness wasremoved on washing.

Another object of the invention is to provide a less Gig-EH20 (4%solids), Polymul 05-81 (a polyethylene emulsion) (2% sollds) and water(94%) was padded onto the fabrics that were cured.

D. These Bil-square cotton fabrics were padded with the solutionidentical as in treatment 0 above with one exception; that is, a freshsupply of Aerotex 238 (a methylated methylolmelamine) was used. Therewas not any difficulty in adjusting the pH of the pad bath when thefresh Aerotex 235 was used.

E. These ESQ-square cotton fabrics were padded in solutions identical totreatment D with one exception; that is, one half of the resin pad$31Zhfiv5 adjusted to pH 4 before padding. The other half was adjustedThe data in Table 11 show that pressure wet-fixation can be accomplishedon a heavier fabric of a more complex construction. As in Table I thedry (or conditioned) complex method for treating or finishing cellulosic75 fabrics treated by the pressure wet-fix method are of relatively lowwrinkle resistance until cured. Treatments C and D show, as the lengthof time that the sealed fabrics remained under pressure was increased,the percent addon, as well as the conditioned and wet wrinkle recoveryangles, increased with an accompanying decrease in the tearing strengthand flex abrasion. Treatment E proved to be an exception, and nosignificant differences occurred lower than conditioned wrinkle recoveryangles. In the pressure wet-fix method, both the conditioned and wetwrinkle recovery angles are essentially the same.

A comparison of pressure wet-fixed fabrics with those from thewet-fixation method in treatment I shows the former is superior inabrasion resistance at the same level of wrinkle resistance.

TABLE II.TWO STEP PADDING METHOD OF PRESSURE WET-FIXATION ON #413 COTTONTWILL Pressure wet-fix, Cure time Cure, Conditioned Tearing Abrasionresis- Air pres- Time in Temp percent at 160 0. percent WRA (w+f) WetWRA strength, gms. tance flex cycles Treatment pH sure, p.s.i. press(min) add-on (min.) add-on deg. (w-l-f) deg. (w.) (w.)

A. These values were obtained on a washed sample of #413 twill which isa white cotton twill.

B. These values were obtained on an unwashed sample of #413 twill.

C. These #413 cotton twill fabrics were padded at p.s.i. pressure in asolution consisting of Aerotex 238 (a methylated methylolmelamine) (10%solids), Penuafresh 183 (a. dimethyloldihydroxyethyleneurea) (10%solids) and water (80%). The solution was adjusted to pH 2 with HCl andallowed to stand 30 minutes at room temperature before padding. Acatalyst-softener solution consisting of MgClrGHzO (4% solids), Polymul08-81 (a polyethylene emulsion) (2% solids) and water (94%) wassubsequently padded onto the fabrics at 30 p.s.i. pressure.

D. These #413 cotton twill fabrics were padded in solutions identical tothose in treatment B; however, the pad pressure was p.s.i., and the padsolution was divided into two equal parts, one being adjusted to pH 4and the other adjusted to pH 6 with NaOH before padding.

E. The #413 cotton twill fabrics were padded at 20 p.s.i. pressure inasolution consisting of Melrez-MF (a methylated methylol-melamine) (10%solids), Permafresh 183 (a dimethyloldihydroxyethyleneurea) (10% solids)and water (80%). The solution was adjusted to pH 2 with HCl and allowedto stand 15 minutes at room temperature before padding. Acatalyst-softener solution consisting of MgCl2-6H2O (4% solids), Polymul08-81 (a polyethylene emulsion) (2% solids) and water (94%) was paddedonto the fabrics at 20 p.s.i. pressure.

when the length of time under pressure was increased. Regardless of thelength of time the sealed fabrics were under pressure, their Stoll flexcycles exceeded those of the controls, which indicated an increase inabrasion resistance. Tearing strength values were not significantlyaltered by variations in time as compared with those of the washed andunwashed controls. In every case the wet wrinkle recovery angle is equalto or exceeds the conditioned wrinkle recovery angle.

The pH of the pad bath has an effect on the final product, butsatisfactory results can be obtained over a range of pH 2 to 6 whenmethylated methylolmelamines, such as Aerotex 23S, Aerotex M-3 andMelrez MF, are used as the polymer builders and adimethyloldihydroxyethyleneurea, such as Permafresh 183, is used as thecrosslinker. When a hexamethoxymethylmelamine such as Cymel 301 is usedas the polymer builder and a dimethyloldihydroxyethyleneurea, such asPermafresh 183, is used as the crosslinker it is necessary to have thepad bath at about pH 4 or lower to obtain satisfactory results.

The overall distribution of properties of pressure wetfixed fabrics isbetter than those produced by treatments well known in the prior art.When a crosslinking resin, catalyst, and softener solution (Treatment H)is padded onto the fabric, dried, and cured, a high conditioned wrinklerecovery angle is obtained. Wet wrinkle recovery angles obtained by thismethod are usually about 20 F. These #413 cotton twill fabrics werepadded at 20 p.s.i. pressure in a solution consisting of Cymel 301 (ahexamethoxyrnethylrnelamine) (10% solids), Permafresh 183 (adimethyloldihydroxyethyleneurea) (10% solids), absolute ethyl alcohol(13.6%) and water (66.4%). The solution was adjusted to pH 2 with HCland allowed to stand 30 minutes at room temperature before padding. Acatalyst-softener solution consisting of MgOlz-(SHeO (4% solids),Polymul 08-81 (a polyethylene emulsion) (2% solids), and water (94%) waspadded onto the fabric at 20 p.s.i. pressure.

G. These #413 cotton twill fabrics were padded in solutions identical tothose in treatment E with one exception; that is, after standing at roomtemperature for 30 minutes, the pad bath was adjusted to pH 6 with N 80Hbefore padding. 4

H. These #413 cotton twill fabrics were padded in a solution consistingof Permafresh 183 (a dimethyloldihydroxyethyleneurea) (18% solids),Zn(NO3)2-6H2O (1% solids) and Polymul 03-81 (1% solids). They were notpressure wet-fixed but were cured in a forced draft oven which is thenormal method used in the prior art.

I. These #413 cotton twill fabrics were padded in a solution consistingof Aerotex 238 (a methylated methylolmelamine) (20% solids), Permafresh183 (a dirnethyloldihydroxyethyleneurea) (20% solids) at pH of 2. Thesefabrics were fixed by the previously mentioned method of the NationalCotton Council. The fabrics were then cured after padding with acatalyst-softener solution composed of Zn(NOa)2-6H2O (0.75% solids) andPolymul 08-81 (1% solids).

Another promising one-step pressure fixation procedure is described bythe descriptions and data in Table III. In this method all pad bathswere at about pH 6 which is the pH resulting on mixing of thecomponents. The pad rolls were set at 20 p.s.i. which gave about 70percent wet pickup. All of the fabrics were pressed at about 27 p.s.i.for 3 minutes with a temperature increase of about from 60 C. or 5minutes with a temperature increase of about from 60 to C. The fabricswere dried for about from 7-10 minutes on removal from the plastic bags.Curing was performed when desired.

This method of pressurewet-fixation produces fabrics with highconditioned and wet wrinkle recovery angles which are of the samemagnitude. Wash-wear ratings were not as high as one would expect offabrics having such high-wrinkle recovery angles. Treatment D wasrepeated with a green sateen fabric and #413 cotton twill. The wash-wearrating of the #413 twill was 4.2 and the wash-wear rating of the greensateen was 5. The tearing strength of the treated fabrics was reducedslightl from that of the washed and unwashed controls. In mosttreatments the Stoll flex cycles were greatly reduced; however, theywere not lower than the conventional treatment G. Cuff laundering testspoint out that the pressure wetfixation method is superior in abrasionresistance to the conventional treatment G as well as the wet-fixationtreatment I.

TABLE LIL-ONE STEP PADDING METHOD OF PRESSURE WET-FIXATION ON #413COTTON TWILL Cure Pressure C ondi- Abrasion W W Rating Cycles Totaldamage time at wet-fix, tloned Wet Tearing resistance to damage after30th wash Treat- 160 C. percent add- W RA WRA strength, flex cycles 1st30th ment (mm on (w+f) (w-i-f) gms.(w.) (w.) wash wash Slight MajorSlight Major A B C 3 5. 21 D 3 10. 45 E-l 3 4. 88 E-2 5 4. 77 F-l 3 9.40 F- 5 9. 15 3. F-3 0. 48 G 7 9. 70 205 4. 2 a. 3 (Hi 7-8 4. 3. 0 15 9.65 159 4. 2 4. 3 3-3 3-4 4. 0 5. 0 H 1, 3 9. 08 522 4. 2 3. 7 11-1522-24 4. (l 5. 0

Percent add-on under treatments G and H are based on the weight of thefabrics before curing.

A. These values were obtained on a washed sample of fabric.

B. These values were obtained on an unwashed sample of fabric.

0. These #413 cotton twill fabrics were padded in a solution consistingof Aerotex M-3 (a methylated methylolmelamine) solids), Permafresh 183(a dimethyloldihydroxy-ethyleneurea) (5% solids), MgClz.6H2O (4%sogidsy)3 Polymul (IS-81 (a polyethylene emulsion) (2% solids), andwater 84 a D. These #413 cotton twill fabrics were padded in a solutionconsisting of Aerotex M-3 (a methylated methylolmelamine) (11.7%solids), Permafresh 133 (a dimethyloldihydroxy-ethyleneurea) (11.7%solids), MgCl'x- GHZO (4.8% solids), Polymul (IS-81 (a polyethyleneemulsion) (2.4%

olids) and the remainder water.

E. These #413 cotton twill fabrics were padded in a solution consistingof Aerotex 238 (a methylated methylolmelamine) (5% solids), Permafresh183 (a dimethyloldihydroxyethyleneurea) (5% solids), MgClzfiH O (4%solidsyL) Polymul 08-81 (a polyethylene emulsion) (2% solids), and Water84 0 EXAMPLE 1 Wrinkle and abrasion resistant cellulosic fabric isproduced in a process whereby 80 x 80 cotton printcloth is padded at 40p.s.i. pressure in a solution of the following composition: percentsolids of a polymer builder of a melamine type resin, methylatedmethylolmelamine (Aerotex 23S), 10 percent solids of a crosslinkingresin, dimethyloldihydroxyethylencurca (Pcrmafresh 183), and 80 percentwater. The solution was adjusted to pH 2 with hydrochloric acid andallowed to stand for minutes at room temperature before adjusting to pH6 with sodium hydroxide before use. Three drops of a wetting agent,alkyl aryl ethylcneoxidc alcohol (Triton X400) were added to the padbath per each 100 grams of solution. After padding, the fabrics wereplaced between sheets of aluminum foil which were folded over to form aclosed or semiclosed container and pressed in a hot-head press for 1minute under 88 p.s.i. pressure with a temperature increase of 60 to 92C. On cooling, the wet fabrics were removed from the aluminum foilcontainers and washed. After drying, the fabrics weer padded at p.s.i.pressure in a solution containing 4 percent solids of a catalyst,magnesium chloride hcxahydrate, 2 percent solids of a softener,polyethylene emulsion (Polymul C5 81), and 94 percent water. The fabricswere dried for 7 minutes at C. in a forced draft oven. The fabrics wereeither cured in a forced draft oven for 3 minutes at 160 C. or storedfor subsequent curing. Results are given in item 04 of Table I.

EXAMPLE 2 Exactly the same as Example 1, except the fabrics were notpadded in the catalyst-softener solution. Results are given in item C-2of Table 1.

EXAMPLE 3 Exactly the same as Example 1, except the time in the presswas 3 minutes with a temperature increase of 60 to 110 C. Results aregiven in item C-3 of Table I.

EXAMPLE 4 Exactly the same as Example 3, except the fabrics were notpadded in the catalyst-softener solution. Results are given in item C-4of Table EXAMPLE 5 Exactly the same as Example 1, except the fabricsremained in the hot-head press for 3 minutes under 27 F. These #413cotton twill fabrics were padded in a solution consisting of Aerotex 238(a methylated methylolmelamine) (10% solids), Permafresh 183 (adimethyloldihydroxyethyleneurea) (10% solids) ,hIgC12.6H2O (4%t,solidis)a Polymul 08-81 (a polyethylene emulsion) (2% solids), and we.er 7 G. These #413 cotton twill fabrics were padded in a solutionconsisting of Permafresh 183 (a dimethyloldihydroxyethyleneurea) (18%solids), MgCl2.6H2O (4% solids) and Polymul CS-Sl (a polyethyleneemulsion) (2% solids). They were not pressure wet fixed but were driedand cured in a forced draft oven which is the normal method used in theprior art.

H. These #413 cotton twill fabrics were padded in a solution consistingof Aerotex 238 (a methylated methylolmelamine) (20% solids), Permafresh183 (a dimethyloldihydroxyethyleneurea) (20% solids) at pH of 2. Thesefabrics were fixed by the previously mentioned method of the NationalCotton Council. The fabrics were then cured after padding with acatalyst-softener solution composed of ZH(NO3) 2.61120 (0.75% solids)and Polymul 08-81 (1% solids).

p.s.i. pressure with a temperature increase of 60 to 110 C. Results aregiven in items 0-5, D-1, and E-3 of Table I.

EXAMPLE 6 Exactly the same as Example 5, except the fabrics were notpadded in the catalyst-softener solution. Results are given in item C-6of Table I.

EXAMPLE 7 Exactly the same as Example 1, except the fabrics remained inthe hot-head press for 5 minutes under 27 p.s.i. pressure with atemperature increase of 60 to 115 C. Results are given in items D-2 and13-4 of Table I.

EXAMPLE 8 Exactly the same as Example 1, except the fabrics remained inthe hot-head press for 7 minutes under 27 p.s.i. pressure with atemperature increase of 60 to 122 C. Results are given in item D-3 ofTable I.

EXAMPLE 9 Exactly the same as Example 1, except the pad bath wasadjusted to pH 4 with sodium hydroxide before use, and the fabricsremained in the hot-head press for 3 minutes under 27 p.s.i. pressurewith a temperature increase of 60 to 110 C. Results are given in itemE-l of Table I.

EXAMPLE 1O Exactly the same as Example 9, except the fabrics remained inthe hot-head press for 5 minutes with a temperature increase of 60 to115 C. Results are given in item E-Z of Table I.

EXAMPLE 1 1 Exactly the same as Example 1 but with the followingexceptions: Style #413 cotton twill (Testfabrics, Inc.) was the fabricused; the pH of the pad bath was allowed to remain at pH 2; the fabricsremained in the hot-head press for 1.5 minutes under 27 p.s.i. pressurewith a tempcrature increase of 60 to C. In addition, the pad pressurewas 30 p.s.i. in both paddings. Results are given in item 0-1 of TableI1.

EXAMPLE 12 Exactly the same as Example 11, except the fabric remained inthe hot-head press for 3 minutes with a temperature increase of 60 to C.Results are given in item C-2 of Table II.

9 EXAMPLE 13 Exactly the same as Example 11, except the fabric remainedin the hot-head press for minutes with a temperature increase of 60 to115 C. Results are given in item C-3 of Table II.

EXAMPLE l4 Exactly the same as Example 11 with the following exceptions:the pH of the pad bath was adjusted to pH 4 with sodium hydroxide beforeuse; the pad pressure was 40 p.s.i. in both paddings; the fabricsremained in the hot-head press for 3 minutes with a temperature increase from 60 to 110 C. Results are given in item D-l of Table II.

EXAMPLE 15 Exactly the same as Example 14, except the time in thehot-head press was 5 minutes with a temperature increase from 60 to 115C. Results are given in item D-2 of Table II.

EXAMPLE 16 Exactly the same as Example 14, except the pH of the pad bathwas adjusted to pH 6 with sodium hydroxide before use. Results are givenin item D-3 of Table II.

EXAMPLE 17 Exactly the same as Example 15, except the pH of the pad bathwas adjusted to pH 6 with sodium hydroxide before use. Results are givenin item D-4 of Table II.

EXAMPLE 18 Wrinkle and abrasion resistant cellulosic fabric is producedin a process whereby Style #413 cotton twill (Testfabrics, Inc.) waspadded at 20 p.s.i. pressure in a solution of the following composition:percent solids of a polymer builder of a melamine type resin, methylatedmethylolmelamine (Melrez MF), 10 percent solids of a crosslinking resin,dimethyloldihydroxyethyleneurea (Permafresh 183), and 80 percent water.The solution was adjusted to pH 2 with hydrochloric acid and allowed tostand for minutes at room temperature before use. Three drops of awetting agent, alkyl aryl ethyleneoxide alcohol (Triton X100), wereadded to the pad bath per each 100 grams of solution. After padding thefabrics were placed in plastic bags, which were self-sealing duringpressing. The fabrics were pressed in a hot-head press for 3 minutesunder 27 p.s.i. pressure with a temperature increase from 60 to 110 C.On cooling, the wet fabrics were removed from the sealed plastic bagsand washed. After drying, the fabrics were padded at p.s.i. pressure ina solution containing 4 percent solids of a catalyst, magnesium chloridehexahydrate, 2 percent solids of a softener, polyethylene emulsion(Polymul CS-81), and 94 percent water. The fabrics were dried for 7minutes at 60 C. in a forced draft oven. The fabrics were either curedin a forced draft oven for 3 minutes at 160 C. or stored for subsequentcuring. Results are given in item E-l of Table II.

EXAMPLE l9 Exactly the same as Example 18, except the time in thehot-head press was 5 minutes and the temperature increase was from 60 to115 C. Results are given in item E2 of Table II.

EXAMPLE 20 Exactly the same as Example 18, except the pad bath so lutionconsisted of 10 percent solids of a melamine type resin,hexamethoxymethylmelamine (Cymel 301), 10 percent solids of acrosslinking resin, dimethyloldihydroxyethyleneurea (Permafresh 183),13.6 percent absolute ethyl alcohol and 66.4 percent water. The solutionwas adjusted to pH 2 with hydrochloric acid and allowed to stand for 30minutes at room temperature before use. Results are given in item F ofTable II.

10 EXAMPLE 21 Exactly the same as Example 20, except the pad bath wasadjusted to pH 6 with sodium hydroxide before use. Results are given initem G of Table II.

EXAMPLE 22 Wrinkle and abrasion resistant cellulosic fabric is producedin a process whereby Style #413 cotton twill (Testfabrics, Inc.) waspadded at 20 p.s.i. pressure in a solution of the following composition:5 percent solids of a polymer builder of a melamine type resin,methylated methylolmelamine (Aerotex M-3), 5 percent solids of acrossliuking resin, dimethyloldihydroxyethyleneurea (Permafresh 183), 4percent solids of a catalyst, magnesium chloride hexahydrate, 2 percentsolids of a softener, polyethylene emulsion (Polymul CS-81), and 84percent water. Three drops of a wetting agent, alkyl aryl ethyleneoxidealcohol (Triton X), were added to the pad bath per each 100 grams ofsolution. The solution was padded at about pH 6, which was the pH of thesolution without alteration. After padding, the fabrics were placed inplastic bags, which were self-sealing during pressing. The fabrics werepressed in a hot-head press for 3 minutes under 27 p.s.i. pressure witha temperature increase from 60 to C. On cooling, the wet fabrics wereremoved from the sealed plastic 'bags and dried 5 minutes at 60 C. in aforced draft oven. The fabrics were either cured in a forced draft ovenfor 3 minutes or stored for subsequent curing. Results are given in itemC of Table III.

EXAMPLE 23 Exactly the same as Example 22, except the percentages of thecomponents in the pad both :were: 11.7 percent Aerotex M3 (a methylatedmethylolmelamine), 11.7 percent Permafresh 183 (adimethyloldihydroxyethyleneurea), 4.7 percent catalyst, 2.4 percentsoftener, and 69.5% water. Results are given in item D of Table III.

EXAMPLE 24 Exactly the same as Example 22, except the melamine typeresin was methylated methylolmelamine (Aerotex 238). Results are givenin item E-l of Table III.

EXAMPLE 25 Exactly the same as Example 24, except the fabric remained inthe press for 5 minutes with a temperature increase from 60 to C.Results are given in item E-2 of Table III.

EXAMPLE 26 Exactly the same as Example 22, except for the composition ofthe pad bath which is of the following composition: 10 percent solids ofa polymer builder of a melamine type resin, methylated methylolmelamine(Aerotex 23S), 10 percent solids of a cross-linking resin,dimethyloldihydroxyethyleneurea (Permafresh 183), 4 percent solids of acatalyst, magnesium chloride hexahydrate, 2 percent solids of asoftener, polyethylene emulsion (Polymul CS-81), and 74 percent water.Results are given in item F-l of Table III.

EXAMPLE 27 Exactly the same as Example 26, except the fabrics remainedin the hot-head press for 5 minutes with a temperature increase from 60to 115 C. Results are given in item -F2 of Table III.

EXAMPLE 28 Exactly the same as Example 26, except the fabric was washedafter drying and was not cured. Results are given in item F-3 of TableIII.

We claim:

1. A process for accomplishing the wet-fixation of resins in cellulosicfabrics comprising the following operations carried out in sequence:

(a) padding the cellulosic fabric to a wet pickup of 1 1 about 80 weightpercent with an aqueous solution containing about from to weight percentof a methylated methylolmela-mine, and about from 5 to 10 weight percentof dimethyloldehydroxyethyleneurea, said aqueous solution being adjustedprior to 1 2 about 4 weight percent of magnesium chloride hexahydrate,and about 2% by weight of emulsified polyethylene. (b) enrobing thepadded cellulosic fabric within a flexible, moisture imperviousmaterial,

the padding operation to pH within the range 2 to 6, 5 (0) imposing apositive pressure of from to (b) enrobing the padded cellulosic fabricwithin a pounds per square inch upon the exterior surfaces flexible,moisture impervious material, of the enrobing material for a period ofabout from (c) imposing a positive pressure of from 20 to 90 1 to 7minutes and at a tem erature of about from pounds per square inch uponthe exterlor surfaces of 10 60 to C.,

the enrobing material for a period of about from (d) removing theenrobing material from the cellulosic 1 to 7 minutes and at atemperature of about from fabric,

'60 to 120 C., (e) drying and then curing the cellulosic fabric from (d)cooling the enrobed cellulosic fabric, step (d) for a period of fromabout 3 to 5 minutes (e) removing the em'obing material from thecellulosic 15 at a temperature of about C.

fabric,

(f) Washing and drying the cellulosic fabric, R f r nces C ted (g;paddting (tge washed and dried Icellulosicfabric UNITED STATES PATENTSrom 5 ep =w1 an aqueous so u 1011 con almng about 4% by weight ofmagnesium chloride hexa- 2O $5.

hydrate and about 2% by weight of emulsified poly- 3o52570 9/1962 3 22;

ethylene, (h) drying and curing the padded cellulosic fabric from g ijstep (g) for a period of from about 3 to 5 minutes at 3245831 4/1966 ggpet a 1 5 3 2 Xempemme abmt i 25 313411955 9/1967 'Pyke etal 117 139.4 X

. process for accomplishing the wet-fixation of 3 374 3/1968 cotton 117139 4 resins in cellulosic fabrics comprising the following operationscarried out in sequence: (a) padding the cellulosic fabric to a wetpickup of about 80 weight percent with an aqueous solution containingabout from 5 to 10 weight percent of a methylated methylolmelamine,about from 5 to 10 weight percent of dimethyloldihydroxyethyleneurea,

WILLIAM D. MARTIN, Primary Examiner 30 T. G. DAVIS, Assistant ExaminerUS. Cl. X.R.

